US5417835A - Solid state ion sensor with polyimide membrane - Google Patents
Solid state ion sensor with polyimide membrane Download PDFInfo
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- US5417835A US5417835A US08/137,373 US13737393A US5417835A US 5417835 A US5417835 A US 5417835A US 13737393 A US13737393 A US 13737393A US 5417835 A US5417835 A US 5417835A
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- polyimide
- integrated circuit
- sensor arrangement
- chemical sensor
- membrane
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/817—Enzyme or microbe electrode
Definitions
- This invention relates generally to devices and systems for measuring concentrations of ions, chemicals, biological materials, and reaction products, and more particularly, to a solid state device which employs a polyimide-based matrix as the substance-sensitive membrane and wherein the substance-sensitive membrane is installed using conventional integrated circuit fabrication techniques.
- Polyimide has been used in the fabrication of integrated circuitry, particularly as a surface protection layer and as a dieleatric material between metal interconnect layers.
- Polyimide films are also known to be flexible, strong, and insoluble.
- the adherence of polyimide to materials which ordinarily are used in the fabrication of such circuit systems to form integrated circuit surfaces is well known. Examples of the materials to which polyimide adheres well include, SiO 2 and Si 3 N 4 . Surfaces formed of these materials are commonly employed in the structure of solid state sensors.
- polyimide exhibits significant mechanical strength, and has been used to provide enhanced mechanical support to certain structures.
- a polyimide layer will form a strong and mechanically rigid coupling between silicon-based materials and structural layers which are relatively weak, such as those formed of boron nitride.
- Polyimide is easily incorporated into the manufacturing processes of integrated circuits. Although it is not photosensitive, it is easily patterned with conventional photoresist, employing a photomask. Moreover, polyimide is easily etched, and mask layers are easily stripped therefrom.
- Silicon and polyimide have been combined in the art to produce a precursor which is useful in the production of a coating which is characterized with a strong adhesion to silicon wafer, glass, etc.
- polyimide precursor improves layer strength and hardness.
- Such precursors have been used as coatings for electronic materials, surface-protecting films, insulating films, and liquid crystal aligning agents.
- Polyimide precursor materials are also known to exhibit superior adhesion onto silicon wafer, glass, or the like, in addition to superior strength and hardness after baking.
- polyimide In addition to its employability as a structural element in the fabrication of integrated circuit systems, polyimide has been used to form porous structures in the form of semipermeable membranes.
- This aspect of polyimide is unrelated to integrated circuit fabrication, and results in the production of asymmetric membranes which have a porosity appropriate for ultrafiltration and reverse osmosis, for example.
- asymmetric membranes are generally prepared by precipitation or phase inversion reaction. The membrane is dissolved in a solvent, spread into a film, and precipitated in a non-solvent. The resulting membrane is suitable for the desalination of sea water.
- asymmetric membranes from polyimides are produced by preparing membranes having asymmetric structures from acid amides of the type which can be converted to polyimides according to conventional precipitation or phase inversion reaction.
- the acid amide membranes are converted subsequently to polyimide membranes by thermal or chemical ring closure reaction.
- One known reaction scheme commences from a tetracarboxylic acid dianhydride and a diamine to form, by means of an acid amide, a polyimide.
- the dianhydride, or an equivalent reaction, such as an acid chloride or the like, and the diamine, in an appropriate solvent, are reacted at room temperature whereby a polyamide is obtained in the form of a soluble polymer.
- the polyamide is then converted to the corresponding polyimide by heating to 300° C. or by chemical reaction.
- polyimides can be made by reaction of dianhydrides with other nitrogen-bearing polyfunctional compounds such as diisocyanates.
- polyimide membranes have been used in other purification processes, such as the purification of crude glyceride oil compositions, whereby the crude glyceride oil composition with impurities in the form of gum material and wax are diluted with an organic solvent and brought into communication with a semipermeable membrane formed of polyimide, under pressure.
- Polyimide membranes of this known type are useful in the removal of impurities which include phospholipids, such as lecithin; waxes, such as higher alcohols; organic sulfur compounds; free fatty acids; peptides; hydrocarbons; carbohydrates; lower aldehydes; lower ketones; dye compounds; and some sterols.
- Polyimide membranes have found wide acceptance in the field of gas separation.
- gas separation membranes include those in which the molecular structure is such that the molecules in the polymer are unable to pack densely, and therefore have high gas permeability; those formed of aromatic polyimide prepared from polyamide acid membranes; those formed from microporous aromatic polyimide membranes, and which optionally are treated with modifying agents; those formed from a microporous aromatic polyimide support coated with an aromatic polyamide acid or aromatic polyimide; those in which the molecular structure is such that the molecules in the polymer can pack densely; those comprising as essential components thereof a saturated linear polyester or polyamide, and having copolymerized therewith benzophenone tetracarboxylic groups which are cross-linked by irradiation; those formed of aromatic polyether imides; those formed from a microporous aromatic polyimide support coated with a cross-linked silicon resin film; and aromatic polyimide reverse osmosis membranes.
- Polyimide membranes which are not
- those aromatic polyimides derived from diamines having substituents on all portions ortho to the amine function or from mixtures of aromatic diamines, particularly where some components have substituents on all positions ortho to the amine functions exhibit high gas permeability.
- Such membranes are in widespread use in systems where it is necessary to select one gas over other gases in a multicomponent gas mixture.
- selectivity is controlled by selection of the amount of aromatic diamines having substituents on all positions ortho to the amine functions, and/or the amounts of structurally-nonrigid dianhydrides utilized in the polyimide preparation while maintaining high gas permeability.
- High permeability is believed in the art to be the result of high molecular free volume in the polymer structure, and is further believed to result from the rigid nature of the rotationally hindered polymer chains.
- polyimide membranes have been used in the context of biological constituents and reaction products.
- a given protein will adhere to a substrate as a monomolecular layer, and that arbitrary protein layers will not adhere to the given protein layer. Instead, a protein which reacts specifically with the given protein will bond immunologically thereto.
- Such reactions have been monitored electronically with the use of a field effect transistor which includes a conventional source and drain, and employs in the gate region a layer of antibody specific to a specific antigen.
- the layer of protein such as the antibodies specific to an antigenic protein to be detected, is adsorbed on a thin insulating layer by immersing the device in a solution of such protein.
- electrochemical devices which are useful in the clinical analysis of biological fluids employ ion-selective membrane layers.
- the ion-selective membrane layer is formed of an ionophoric material which is dispersed in a matrix of dielectric organic polymer.
- the matrix polymer is combined with a plasticizer to effect a certain amount of swelling of the polymer. This is oftentimes necessary to permit sufficient mobility of ion carriers through the membrane.
- plasticizers which have been used in such applications are dioctyl adipate, tris(2-ethylhexyl)phosphate, dibutyl sebacate, O-nitrophenyloctyl ether, diphenyl ether, dinonyl phthalate, dipentyl phthalate, di-2-nitrophenyl ether, glycerol triacetate, tributyl phosphate, and dioctyl phenyl phosphate.
- the ion-selective membranes are usually made by forming a solution of polymer, and optionally a plasticizer, in a volatile organic solvent, casting the solution onto the desired surface into the desired shape, and then removing the solvent by evaporation.
- One prior art method for producing a substance-sensitive device which can be fabricated using conventional mass production technology employs a substance-sensitive photoresist layer which is compatible with large scale integrated circuit technology.
- a substance-sensitive photoresist layer which is compatible with large scale integrated circuit technology.
- small quantities of substance-sensitive materials are dissolved and then fixed in the photoresist material by the exposure or non-exposure, to particular radiations, depending upon the type of photoresist.
- a photoresist material is doped with a substance-sensitive material, and subsequently activated, a substance-sensitive layer will remain on the surface of the structure to which the photo-resist material is initially applied.
- those polymer membranes which exhibit the preferred electrochemical properties are typically also those which are most incompatible with large scale integrated circuit fabrication.
- such membranes do not adhere well to the silicon-based substrate, and are not readily adapted to mask based or photolithographic dimensioning techniques.
- such systems are not generally applicable to a multiplicity of solid state sensors simultaneously, such as at the wafer stage of production.
- the integrated circuit sensor be provided with a suspended mesh of polyimide.
- the polyimide is known to adhere well to the silicon-based substrate, and a polymeric membrane is formed in the void between the polyimide and the substrate by insertion while the polymeric membrane is in liquid form.
- Other systems have been proposed which utilize polyimide as a structural element for holding and/or supporting an ion-selective membrane in communication with the integrated circuit. All of these approaches to the basic problem of incompatibility of the membranes to solid state fabrication techniques require complex post IC manufacturing steps, often requiring manual operations, and yield results which are not reproducible from sensor to sensor.
- a still further object of this invention is to provide a substance-sensitive membrane for use in a solid state sensor, wherein the membrane exhibits good adhesion to SiO 2 surfaces.
- An additional object of this invention is to provide a substance-sensitive membrane for use in a solid state sensor, wherein the membrane exhibits good adhesion to Si 3 N 4 surfaces.
- this invention provides an integrated circuit chemical sensor arrangement having an input electrode formed of a conductive material in the vicinity of a region formed of a silicon-based semiconductor material, the integrated circuit chemical sensor arrangement being provided with a permselective membrane having a predetermined electrochemical property.
- the permselective membrane is formed of a polyimide-based compound arranged to be in adherence with the silicon-based semiconductor material and in electrical communication with the input electrode, whereby the permselective membrane produces at the input electrode a voltage responsive to the electrochemical property.
- the permselective membrane is formed of a polyimide powder which is dissolved in a solvent.
- the solvent may be N,N-dimethylformamide (DMF).
- a plasticizer which may be diethylene glycol dibenzoate, is mixed with the dissolved polyimide powder. In some embodiments, a further plasticizer may be employed, such as dipentyl phthalate.
- a lipophilic additive is combined with the mixture.
- Such an additive may be potassium tetrakis(p-chlorophenyl)borate.
- the electrochemical property of the integrated circuit chemical sensor arrangement on the present invention is responsive, in a specific embodiment thereof, to an ionophore.
- the ionphore is the chemical which is added to the membrane to give it the desired electrochemical property.
- the ionophore may be a calcium ionophore, such as ETH 129 and ETH 1001.
- the chemical sensor arrangement may have an electrochemical characteristic which is responsive to a different ionophore, such as an ammonium ionophore (nonactin).
- inventions may have electrochemical properties which are responsive to biological agents or reaction products of biological processes.
- the electrochemical properties may be responsive to an enzyme, an immunochemical, a bacteria, a virus, an antibody, an antigen, etc.
- the integrated circuit chemical sensor arrangement of the present invention is suitable for use in the detection of substances of clinical interest.
- the permselective membrane is comprised of a preimidized material, such as an encapsulant denominated as PI-2590-D, which is commercially available from DuPont.
- a plasticizer such as diethylene glycol dibenzoate (DGD) and/or dipentyl phthalate (DPP) mentioned hereinabove, are mixed with the encapsulant.
- DPD diethylene glycol dibenzoate
- DPP dipentyl phthalate
- a lipophilic additive such as potassium tetrakis(p-chlorophenyl)borate
- an ionophore or a bioactive agent, is additionally added to provide the desired electrochemical property. An ionophore is always required. However, the bioactive layer is optional.
- a substance-sensitive membrane for a solid state sensor arrangement is produced by the steps of dissolving a polyimide in a solution, mixing an ionophore into the dissolved polyimide, mixing a plasticizer into the dissolved polyimide, and mixing a lipophilic additive into the dissolved polyimide.
- a polyimide powder is dissolved in a solvent, such as N,N-dimethylformamide (DMF).
- a solvent such as N,N-dimethylformamide (DMF).
- the polyimide which is dissolved is the polyimide encapsulant known as PI-2590-D, wherein the solvent therein is N-methyl-2-pyrridone.
- DMP and/or DGG are added as plasticizers, and a lipophilic additive, such as potassium tetrakis(p-chlorophenyl)borate is also added.
- a film is produced by depositing the desired polyimide with the ionophore, the plasticizer(s), and the lipophilic additive mixed therein onto a substrate.
- the substrate may be, for example, the integrated circuit which forms the remainder of the solid state sensor, or a glass substrate from which the film membrane will be removed.
- the solvent is removed from the deposited polyimide, illustratively by subjecting same to a vacuum.
- an active agent is added to the mixture, which agent is an ionophore, such as a calcium ionophore, or an ammonium ionophore, an optional biologically active agent or other substance-sensitive agent, may be added as discussed herein.
- a substance-sensing membrane for a solid state sensor is formed of a mixture of polyimide dissolved in a solvent, an ionophore for determining the substance-sensitive electrochemical property of the substance-sensitive membrane, a plasticizer selected from the group of dimethyl phthalate and diethylene glycol dibenzoate, and potassium tetrakis(p-chlorophenyl)borate as a lipophilic additive.
- FIG. 1 is a graphical representation of the response of a calcium-selective membrane, as measured on an ion-selective electrode body;
- FIG. 2 is a graphical representation of a calibration curve for an ammonium-selective polyimide membrane, which illustrates the selectivity of ammonium over sodium.
- FIG. 3 is a graphical representation of the potentiometric response of a polyimide membrane constructed in accordance with the invention, toward ammonium ions;
- FIG. 4 is a graphical representation of the potentiometric response of a polyimide membrane toward ammonium ions, the membrane having an increased amount of lipophilic additive and mixed plasticizer;
- FIG. 5 is a graphical representation of the potentiometric response of PVC-based membranes formed using DGD as the plasticizer
- FIG. 6 is a graphical representation of a comparison of the potentiometric response of the polyimide membrane to those of conventional PVC and liquid-type Ca 2+ -selective electrodes.
- FIG. 7 is a graphical illustration of the adhesion characteristics of the polyimide membranes as compared to PVC membranes.
- a first polyimide membrane composition constructed in accordance with the principles of the invention is as follows:
- FIG. 1 is a graphical representation of the response of this calcium-selective membrane, as measured on an ion-selective electrode body. This figure shows the polyimide membrane response compared to a commercial liquid-junction electrode and to a commercial PVC-based ISE.
- FIG. 2 is a graphical representation of a calibration curve for polyimide membrane composition 2. This figure illustrates the response of the membrane of composition 2 to sodium, and demonstrates that the selectivity of the membrane for ammonium over sodium is comparable to that of PVC-based membranes.
- the polyimide membranes of compositions 1 and 2 were formed by solvent casting on glass. The membranes were then installed on a ion-selective electrode body for electrochemical characterization.
- the polyimide membranes exhibited outstanding properties of adhesion to glasses. Moreover, these films exhibit excellent stability, and have been shown through experimentation to retain 90% of their initial tensile strength after 1000 hours at 300° C.
- the membranes are resistant to most organic solvents, and are degraded somewhat by aqueous acids and alkalis.
- membranes are those which contain ionophore to a specific ion.
- a bioactive agent such as an enzyme, an immunochemical, a bacteria, etc. The introduction of such agents into the membrane will result in specificity for complex chemicals.
- the measurements of the potentiometric characteristics of the membranes was performed by mounting the membranes in Phillips electrode bodies (IS-561)(Glasblaserei Moller, Zurich).
- the external reference was an Orion sleeve-type double junction Hg/AgCl electrode (Model 90-02).
- the electrodes were connected through a high impedance amplifier to a Zenith Z-100 personal computer equipped with an analog-to-digital converter (DT 2801, Data Transaction Inc., Marlborough, Mass.).
- poly(vinyl chloride) high molecular weight (PVC); dibutyl sebacate (DBS); o-nitrophenyl octyl ether (o-NPOE); nonactin; calcium ionophore II (ETH 129); and potassium tetrakis(p-chlorophenyl)borate (KTpCIPB) were obtained from Fluka (Ronkonkoma, N.Y.); polyimide (PI--fully imidized and polymerized); plasticizer sample kit 301 (90 different plasticizers, including dimethyl phthalate (DMP) and diethyl glycol dibenzoate (DGD)) were purchased from Scientific Polymer Products, Inc.
- DMP dimethyl phthalate
- DTD diethyl glycol dibenzoate
- Polyimide-based ion-selective membranes were formed by dissolving polyimide (PI) powder in DMF (25% w/w) by heating the solution to 120° C.
- PI polyimide
- Various membranes having different compositions were then prepared by mixing the PI solution with membrane active components, including ionophore, plasticizer, and lipophilic additives. The mixture was applied dropwise to a glass plate, and the solvent (DMF) was allowed to evaporate for two days under vacuum.
- the membranes which employed the PI-2590-D polyimide encapsulant were formed by mixing the encapsulant directly with the membrane active components and applying same to the glass plate. In this case, however, longer evaporation periods, on the order of 4-5 days, were employed as a result of the high boiling point of the solvent (N-methyl-2-pyrrolidone) which is used in PI-2590-D.
- PVC-based ion-selective membranes were formed by incorporating nonactin and ETH 129, respectively, into PVC membranes.
- the preparation of such membranes is known to persons skilled in the art.
- the inner filling solution varied, depending upon which ion-selective membrane was being evaluated. For example, 0.1 M NH 4 Cl was used for NH 4 + -selective membranes, and 0.01 M CaCl(2) was used for Ca 2+ -selective membranes.
- the calibration plots were obtained from additions of standard solutions to 250 ml of background electrolyte (0.05M Tris-HCl having pH 7.2) at room temperature. The selectivity coefficients were determined by the known separate solution method.
- Adhesion characteristics were evaluated using a known method. For each membrane type, ten membranes were cast by drops onto a silicon wafer coated with 10,000 ⁇ of plasma-deposited silicon nitride. In the case of the polyimide membranes, an adhesion promoter (VM-651, DuPont Company, Wilmington, Dela.) was applied to the wafer before casting the membranes. After the membranes were cured, the wafers were immersed in an ultrasonic bath (Branson Cleaning Equipment, Smithkline Company, Shelton, Conn.), the time to detachment was recorded for each membrane.
- an ultrasonic bath Branson Cleaning Equipment, Smithkline Company, Shelton, Conn.
- plasticizers which are frequently used in the preparation of PVC-based ion-selective membranes such as DBS, DOA, o-NPOE, etc.
- DMP dimethyl phthalate
- DLD diethylene glycol dibenzoate
- Incorporation of these plasticizers into the polyimide matrix appeared to have little effect on the excellent adhesion properties of the resulting membranes toward glass surfaces. As indicated, these membranes can not be pulled free from the glass, but must be cut from the glass plate with a razor blade.
- nonactin (2 mg) was incorporated into polyimide-matrix membranes (75 mg of PI) along with a plasticizer, DMP or DGD (130 ⁇ l).
- FIG. 3 is a graphical representation of the potentiometric response of a polyimide membrane constructed in accordance with the invention toward ammonium ions.
- the polyimide membrane prepared with DGD exhibited better response characteristics, i.e, lower detection limits, than that prepared with DMP.
- the response characteristic of the DGD-based polyimide membranes exhibited a slope 50 mV per decade or 10 -5 to 10 -2 moles NH 4 + . This characteristic is inferior to those membranes which are PVC-based.
- PI-2590-D encapsulant was used in these membranes.
- An increase in the amount of lipophilic additive (KTpCIPB) in the membrane phase increased the response slope of the resulting PI-2590-D matrix membrane.
- This improvement in the response is evident in the graphic representation of FIG. 4.
- This figure is a graphical representation of the potentiometric response of a polyimide membrane toward ammonium ions, the membrane having an increased amount of lipophilic additive.
- the potentiometric response was further improved when the membrane was prepared by using an additional plasticizer, dipentyl phthalate (DPP), which previously had been used for the preparation of the NH 4 + -selective polymer membranes.
- DPP dipentyl phthalate
- FIG. 5 illustrates that PVC-based membranes prepared using DGD as the plasticizer had significantly degraded response toward NH 4 + . As shown in FIG. 5, this membrane exhibits a slope of 47.3 mV per decade over the range of 10 -5 to 10 -1 M NH 4 + . However, the optimized PI-2590-D membranes exhibited nearly the same response slope (56.5 mV per decade) as those found for the conventional PVC-based membrane (56.9 mV per decade).
- the polyimide matrix was further evaluated by preparing Ca 2+ -selective membranes. For this, ETH 129 (2 mg) was incorporated with KTpCIPB (1.2 mg), DGD (66 ⁇ l), and polyimide (PI 66 mg).
- FIG. 6 is a graphical representation of the potentiometric response of the polyimide matrix membrane, compared to those of conventional PVC and commercial Orion liquid-type Ca 2+ -selective electrodes. The performance of these electrodes is seen to be comparable except for a slightly higher detection limit for the polyimide matrix membrane.
- FIG. 7 is a graphical illustration of the adhesion characteristics of the polyimide membranes, as compared to PVC membranes. As shown, detachment of the ten PVC membranes occurred over a range of 25 to 60 minutes, with the median time being 31 minutes. Five polyimide membranes detached almost in unison between 9 hours and 37 minutes and 9 hours and 40 minutes. The remaining five remained intact when the test was terminated after 24 hours. The median polyimide membrane lifetimes in this test were, therefore, more than 25 times longer than that of the PVC membranes.
Abstract
Description
______________________________________POLYIMIDE MEMBRANE COMPOSITION 1 ______________________________________ PI 32.8 wt % polyimide dissolved in poly(amic) acid DGD 65.6 wt % plasticizer - diethylene glycol diben- zoate KTpCIPB 0.6 wt % lipophilic additive - potassium tetrakis(p-chlorophenyl) ETH 129 1.0 wt % calcium ionophore ______________________________________
______________________________________POLYIMIDE MEMBRANE COMPOSITION 2 ______________________________________ PI-2590 600 mg preimidized polyimide encapsulant (DuPont)DGD 50 μl plasticizer - diethylene glycol diben-zoate DPP 50 μl plasticizer - dipentyl phthalate KTpCIPB 0.67 mg lipophilic additive - potassium tetrakis(p-chlorophenyl)Nonactin 2 mg ammonium ionophore ______________________________________
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US08/137,373 US5417835A (en) | 1989-06-23 | 1993-10-14 | Solid state ion sensor with polyimide membrane |
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US37089789A | 1989-06-23 | 1989-06-23 | |
US74613491A | 1991-08-13 | 1991-08-13 | |
US08/137,373 US5417835A (en) | 1989-06-23 | 1993-10-14 | Solid state ion sensor with polyimide membrane |
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Cited By (18)
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US5607567A (en) * | 1992-03-10 | 1997-03-04 | The Board Of Regents Acting For And On Behalf Of University Of Michigan | Protamine-responsive polymeric membrane electrode |
US5837446A (en) * | 1988-11-14 | 1998-11-17 | I-Stat Corporation | Process for the manufacture of wholly microfabricated biosensors |
EP0999055A2 (en) | 1998-11-03 | 2000-05-10 | Samsung Electronics Co., Ltd. | Micro injecting device and method of manufacturing the same |
US6214185B1 (en) * | 1997-04-17 | 2001-04-10 | Avl Medical Instruments | Sensor with PVC cover membrane |
US6306594B1 (en) | 1988-11-14 | 2001-10-23 | I-Stat Corporation | Methods for microdispensing patterened layers |
US20020031843A1 (en) * | 1999-01-20 | 2002-03-14 | Harmon H. James | Broad spectrum bio-detection of nerve agents, organophosphates, and other chemical warfare agents |
US6451191B1 (en) * | 1999-11-18 | 2002-09-17 | 3M Innovative Properties Company | Film based addressable programmable electronic matrix articles and methods of manufacturing and using the same |
US20030203187A1 (en) * | 1999-12-27 | 2003-10-30 | Kodak Polychrome Graphics,Llc | Manufacture of masks and electronic parts |
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US20060020427A1 (en) * | 2004-05-07 | 2006-01-26 | Sensicore, Inc. | Systems and methods for fluid quality monitoring using portable sensors in connection with supply and service entities |
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US9562885B2 (en) | 2013-05-17 | 2017-02-07 | Umm Al-Qura University | Ionophore and polymer membrane selective for aluminum (III) ion |
RU2736488C1 (en) * | 2020-03-19 | 2020-11-17 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Composition of ion-selective electrode membrane for determination of calcium ions |
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US6306594B1 (en) | 1988-11-14 | 2001-10-23 | I-Stat Corporation | Methods for microdispensing patterened layers |
US5837446A (en) * | 1988-11-14 | 1998-11-17 | I-Stat Corporation | Process for the manufacture of wholly microfabricated biosensors |
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